WO2004033561A1

WO2004033561A1 - Non-flak coated colouring pigment and method for the production and use thereof

Info

Publication number: WO2004033561A1
Application number: PCT/EP2003/010552
Authority: WO
Inventors: Armin Kuebelbeck; Jens Eichhorn
Original assignee: Merck Patent Gmbh
Priority date: 2002-10-08
Filing date: 2003-09-23
Publication date: 2004-04-22
Also published as: AU2003271634A1; KR20050048677A; US20060014019A1; EP1551925A1; JP2006502262A

Abstract

The invention relates to a non-flak coated colouring pigment consisted of organic or inorganic, amorphous or partially crystalline material provided at least with one coating. Each layer contains at least cured melamine-formaldehyde resin or consists thereof. The inventive pigment is successfully used for producing cosmetic products and confers a pleasurable sensation to the user thereof.

Description

Coated, non-platelet colored pigment, process for its preparation and its use

The invention relates to a coated, non-platelet-shaped color pigment, a process for its production and its use. The invention also relates to compositions containing such a pigment.

Cosmetic products often contain pigments to give them a colored look. Some of these pigments give the user of the cosmetic products a dull, dry and therefore unpleasant feeling on the skin. This is particularly the case for pigments based on iron (πi) hexacyanoferrate (H), which is also known as Berlin blue, or chromium (πi) oxide.

It is an object of the present invention to provide color pigments, in particular for cosmetic products and other products which are applied to the skin, which impart a pleasant feeling on the skin.

Surprisingly, it has been found that this object can be achieved by coating the color pigments with a hardened melamine-formaldehyde resin.

Coated pigments are generally known. EP-A-0 601 378 describes platelet-shaped mica pigments coated with melamine resin. These pigments are used as effect pigments in metallic paintwork for automobiles, and the purpose of the coating is to improve the storage stability of the paints and the surface properties of the resulting paint film.

DE-A-197 10 619 discloses solid particles coated with melamine resin, to which impregnating resin solutions are added for the production of laminates in order to improve the abrasion resistance of the wood-based materials coated with the laminates. The core of the coated solid particles consists of quartz, nitride, carbide. These are not color pigments. The present invention relates to a coated, non-platelet-shaped color pigment, which is characterized in that the pigment consists of an inorganic or organic, amorphous or partially crystalline material which is provided with at least one coating, each layer comprising at least one hardened melamine-formaldehyde Contains or consists of resin. Cosmetic products and other products that are applied to the skin give the user a pleasant feeling on the skin if they contain a color pigment according to the invention.

The pigment is advantageously iron (_ π) hexacyanoferrate (II) or chromium (IH) oxide. However, other pigments can also be coated in the same way with a hardened melamine-formaldehyde resin. These are, for example, titanium (IV) oxide, zirconium (IV) oxide, and oxides of iron such as magnetite and hematite.

In the case of the crosslinked melamine-formaldehyde resins, some of the melamine molecules can also be replaced by other crosslinkable molecules, such as, for example, phenols, guanamines or urea. The melamine-formaldehyde resins can be unetherified or etherified melamine-formaldehyde adducts, for example alkoxymethylol-melarnines with C ₁ -C ₆ -alkoxy groups, such as methoxy or n-butoxy groups, and precondensates. Examples include Madurit MW 909 as unetherified resin or Madurit SMW 818 as etherified resin (both products from Solutia, Wiesbaden, Germany). Some of the melamine-formaldehyde resin can also be replaced by other crosslinking organic polymers. Particularly suitable are those which also have a high refractive index, particularly those which have a refractive index which is greater than that of the uncoated pigment.

By coating the pigment with melamine-formaldehyde without the addition of colorants, the inherent color of the pigment changes depending on the thickness of the coating. As the thickness of the coating increases, the color impression shifts towards lighter and paler colors. For those for the more pleasant 1-tautgeτunι necessary coating thicknesses, the effect of brightening is hardly noticeable to the eye.

Of course, the lightening does not apply to colorless pigments, such as titanium (IV) oxide or zirconium (IV) oxide.

In contrast to platelet-shaped pigments, no interference color that can be adjusted by the coating thickness is formed when coating with melamine-formaldehyde. This is essentially due to the very uneven surface of non-platelet-shaped pigments, which prevents a uniform layer thickness to form interference.

Any organic and inorganic dyes as well as optionally colorless UV absorbers can be incorporated into the melamine-formaldehyde resins. The only decisive factor for incorporation into the polymer matrix is its solubility in the medium in which the coating reaction is carried out. Even water-soluble dyes such as eosin, fluorescein or Victoria Pure Blue BO can be embedded in the polymer matrix without bleeding out later. For lipophilic dyes, the coating reaction can also be carried out in an aqueous medium if the solubilizers familiar to the person skilled in the art are added. 1-methyl-2-pyrrolidone can be mentioned here as an example of a solubilizer.

The usual principles of additive color mixtures can be used to obtain color nuances. The color tones can be adjusted by mixing the dyes in advance and introducing them together into a polymer layer or by applying several dye-polymer layers to the inorganic substrate one after the other so that layers of different colors overlap.

Acidochromic dyes, that is, dyes whose color depends on the pH value, can essentially be incorporated into the melamine-formaldehyde resin while maintaining the color tone and color change point. Examples include phenolphthalein, bromothymol blue, bromxylene blue and thymolphthalein. In addition to the fluorescein already mentioned, other fluorescent dyes, optical brighteners or other UV light-absorbing dyes can also be incorporated into the polymer matrix.

In particular, the installation of several dyes is recommended, at least one of which is a fluorescent dye. The incorporation of at least two fluorescent dyes is particularly advantageous, the second fluorescent dye being added in considerably smaller amounts. As a result, pigments can be obtained whose resulting fluorescent color differs significantly from the fluorescent color of the starting materials. In this way it is possible to easily synthesize a large number of differently fluorescent pigments. A wide range of fluorescent colors can be produced by varying the type of the fluorescent dye or dyes and varying the second dye, added in considerably smaller amounts, both with regard to the type and the concentration. Often, these pigments appear very inconspicuous and comparatively pale in visible light due to the low proportion of color-determining dyes. In addition to the basic colors red, green and blue, well over a hundred different fluorescent colors that can be clearly distinguished by the eye can be realized.

By depositing a polymer layer containing one or more fluorescent dyes on a polymer layer that has already been applied beforehand, the brilliance and luminosity of the pigments can be significantly increased. In addition, fading of the layers underneath can be inhibited by the absorption of the UV light. Such UV protection can also be achieved by incorporating UV absorbers into the polymer layer containing the dye itself.

In principle, all UV filters can be used as suitable UV absorbers. Those UV filters whose physiological safety has been proven are particularly preferred. For UV-A as well as UV-B filters, there are many well-known and proven substances from the specialist literature. Here, for example, benzylidene camphor derivatives, such as 3- (4'-methylbenzylidene) -dl camphor, 3-benzylidene camphor, polymers of N - {(2 and 4) - [(2-oxoborn-3-ylidene) methyl] benzyl} acrylamide, N, N, N-trimethyl-4- (2-oxoborn-3-ylidene methyl) anilinium methyl sulfate or α- (2-oxobom-3-ylidene) toluene-4-sulfonic acid, benzoyl or dibenzoyl methanes such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propan-1, 3-dione or 4- isopropyldibenzoylmethane,

Benzophenones such as, for example, 2-hydroxy-4-methoxybenzophenone or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, methoxycinnamic acid esters such as octyl methoxycinnamate, isopentyl 4-methoxycinnamate and its isomer mixture, salicylate derivatives such as, for example

2-ethylhexyl isalicylate, 4-isopropylbenzyl salicylate or

3,3,5-trimethylcyclohexyl,

4-aminobenzoic acid and its derivatives such as 4- (dimethylamino) benzoic acid-2-ethylhexyl ester or ethoxylated 4-aminobenzoic acid ethyl ester, as well as other substances such as 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester, 2-phenylbenzimidazole-5-sulfonic acid as well as their potassium, sodium and triethanolamine salts, 3,3 '- (1,4-phenylenedimethylene) -bis- (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-ylmethanesulfonic acid and their Salts and 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1 ^' -oxy) -1, 3,5-triazine.

Other suitable organic UV filters are, for example

2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1, 3,3,3-tetramethyl-1-

(trimethylsilyloxy) disiloxany!) propyl) phenol, 4,4 ^' - [(6- [4 - ((1, 1-dimethylethyl) aminocarbonyl) phenylamino] -1, 3,5-triazine-2,4-diyl) diimino ] bis (2-ethylhexyl benzoate), α- (trimethylsilyl) -ω- [trimethylsilyl) oxy] poly [oxy (dimethyl [and about 6% methyl [2- [p- [2,2- bis (ethoxycarbonyl] vinyl] phenoxy] -1-methyleneethyl] and about 1.5% methyl [3- [p- [2,2- bis (ethoxycarbonyl) vinyl) phenoxy) propenyl) and 0.1 to 0.4% ^' ( methylhydrogenjsilylen]] (n »60) (CAS No. 207 574-74-1), 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1, 3,3-tetramethylbutyl) phenol), 2,2 ^' - (1,4-phenylene) bis- (1H-benzimidazole-4,6-disulfonic acid, monosodium salt) and 2,4-bis - {[4- (2- Ethyl hexyloxy) -2-hydroxyl] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine. Preferred compounds with UV-absorbing properties are 3- (4'-methylbenzylidene) dl-camphor, 1 - (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, 4-isopropyidibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethylcyclohexyl salicylate, 2-ethylhexyl 4- (dimethylamino) benzoate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-phenylbenzimidazole-5 -sulfonic acid and its potassium, sodium and triethanolamine salts.

The protective effect against harmful effects of UV radiation can be optimized by combining several UV filters.

The coated color pigments can be produced by depositing crosslinking melamine-formaldehyde resins on the suspended pigments and then curing, that is to say crosslinking, the melamine-formaldehyde resins.

The process according to the invention for producing a single or multiple-coated color pigment comprises, in the case of a single coating, a first step in which a color pigment is suspended in a basic aqueous medium, containing melamine and formaldehyde and / or methylolmelamine, which can optionally be alkoxylated, and a second step in which brings about a crosslinking of the organic constituents by lowering the pH in the acidic range and, in the case of a multiple coating, the first and second steps are repeated with the product of the preceding coating process.

It has been found that it is particularly advantageous to bring about the lowering of the pH in the second process step by adding hydrogen peroxide by oxidizing excess or unreacted formaldehyde from the first process step to formic acid. Since formaldehyde is problematic in cosmetic applications, a pigment can be provided which is free of free formaldehyde molecules and therefore cosmetic is not feasible. This also works with methyloimelamines, since they usually still contain sufficient amounts of free formaldehyde.

In the process according to the invention, part of the melamine can be replaced by other crosslinking molecules from the group consisting of "guanamines, phenols and ureas" and / or part of the methylolmelamine by corresponding guanamine, phenol or urea analogues.

Before or during the crosslinking reaction, inorganic or organic dyes and / or inorganic or organic UV absorbers can be added.

If the dyes or UV absorbers do not completely dissolve in the aqueous medium, a complete solution can be brought about by solubilizers. This is especially true when using lipophilic substances.

The layer thickness of the coating can be controlled by the melamine-formaldehyde resin concentration. This means that thicker layers are obtained at high concentrations than at low concentrations. The pH value is also a suitable means of controlling the layer thickness. Low pH values lead to thinner coatings. DE 1595386 also describes the control of layer thicknesses by the addition of protective colloids.

Preferred total layer thicknesses of single or multiple coated substrates are preferably 0.2 μm to 4 μm.

By using excess melamine-formaldehyde resin, additional, essentially round melamine-formaldehyde resin particles can be deposited on the outermost coating, which in addition to organic dyes can also contain UV absorbers or are completely free of dyes or UV absorbers.

Depending on the reaction, the number of balls per color pigment particle, the ball diameter and the distribution of the ball diameter (dispersity) to be controlled. For cosmetic purposes in particular, a certain proportion of spheres is advantageous for an improved skin feel.

However, too high a proportion of spheres reduces the brilliance and the appearance of the pigment. If there is a sufficient proportion of dye, the additional spheres have a color matching the color pigments.

The space-time yield relevant from the point of view of economy can be increased significantly by adding polymers with strongly acidic groups, as is described, for example, in EP 0415273.

For certain applications, it may be advantageous to incorporate functional groups other than the strongly acidic groups mentioned in the condensation product of the outermost layer of the polymer, in order to improve them, for example, with regard to their binder compatibility and the dispersion behavior. It is also possible to provide the outermost layer of the crosslinked organic polymer with functional groups by subsequently reacting the melamine-formaldehyde resins. DD 224 602 describes various possibilities for functionalizing resins.

Functional groups in the sense of this invention can be any hydrophilic or hydrophobic, acidic or basic groups. B. also purely hydrophobic largely inert groups such. B. Alcyl groups.

According to one of the processes described in DD 224 602, functional groups are incorporated into the surface of the polymer particles in which the polycondensation reaction of the melamine-formaldehyde resin takes place in the presence of amino-functional compounds, the amino-functional compounds carrying further functional groups in addition to the amino group. The amino-functional compounds are added in amounts of preferably 2 to 20 mol percent, based on the amount of methylolmelamine used, and are incorporated into the melamine-formaldehyde network via the amino function. So z. B. when using amino acids carboxyl groups or in the case of sulfobetaines or aminophosphonic acids sulfo or phosphonic acid groups build into the surface of the particles. Such -COOH, -S0 ₃ H or -PO ₂ H groups can in turn be reacted with other compounds. For example, the acid groups can be converted into corresponding acid chlorides by reaction with tionyl chloride, which in turn can be reacted with alcohols or amines, for example, the corresponding esters or amides being formed. This process of surface modification is characterized by its simplicity, since the melamine-formaldehyde resin surface is immediately functionalized in a slightly modified condensation process. However, it can be disadvantageous that the corresponding functionalities are also incorporated into the polymer volume by the condensation process and thus the adhesion to the layers underneath or, in the case of a single-layer structure, the adhesion to the substrate can be reduced. On the other hand, with a corresponding selection for certain systems, the adhesion to the underlying layers or to the substrate can be increased if groups are introduced by the surface modification agent that both improve the compatibility with the surrounding medium and also adhere to the underlying layers or convey the substrate. In this method, however, relatively large amounts of the surface-functionalizing agent are required due to the incorporation into the melamine-formaldehyde network. More complex chemical functionalities are also difficult to obtain through simple installation during polycondensation.

Another method for surface functionalization is therefore based on a finished polycondensed melamine-formaldehyde surface which has free, non-crosslinked methylolamine (NH-CH ₂ OH) or amino groups. These groups can be reacted in a simple manner, for example with carboxylic acid chlorides. So z. B. when using long-chain carboxylic acid chlorides, a hydrophobization of the pigment can be achieved. With perfluorinated acid chlorides such as. B. Per-fluoroctanoic acid, both hydrophobic and lipophobic surfaces can be obtained. By using complex acid chlorides, which e.g. B. may contain strong UV light absorbing groups, the melamine-formaldehyde surface can also further functionalities, for. B. contain UV protection. Advantageous embodiments of the invention result from the subclaims.

The invention also relates to compositions and cosmetic preparations which contain one or more of the coated non-platelet-shaped carrier materials as a color pigment.

Of course, the coated, non-platelet-shaped color pigments according to the invention can also be combined in the compositions or preparations with any type of cosmetic raw materials and auxiliaries. These include Oils, fats, waxes, film formers, preservatives and auxiliary substances that determine general application properties, e.g. Thickeners and rheological additives such as bentonites, hectorites, silicon dioxide, calcium silicates, gelatins, high-molecular carbohydrates and / or surface-active agents etc.

The formulations containing the color pigments according to the invention can be of the lipophilic, hydrophilic or hydrophobic type. In the case of heterogeneous formulations with discrete aqueous and non-aqueous phases, the color pigments according to the invention can each contain only one of the two phases or else be distributed over both phases.

The pH values of the formulations can be between 1 and 14, preferably between 2 and 11 and particularly preferably between 5 and 8.

There are no limits to the concentrations of the color pigments according to the invention in the formulation. Depending on the application, they can be between 0.001 (rinse-off products, e.g. shower gels) - 100% (e.g. gloss effect articles for special applications).

The color pigments according to the invention can also be combined with cosmetic active ingredients. Suitable active ingredients are, for example, insect repellents, UV ^'A / BC protective filters (for example OMC, B3, MBC), anti-aging active ingredients, vitamins and derivatives thereof (for example vitamin A, C, E, etc.), self-tanning (for example DHA, Erytrolose and others) as well as other cosmetic active ingredients such as bisabolol, LPO, ectoin, emblica, allantoin, bioflavanoids and their derivatives. The preparations are usually topically applicable preparations, for example cosmetic or dermatological formulations. In this case, the preparations contain a cosmetically or dermatologically suitable carrier and, depending on the desired property profile, optionally further suitable ingredients.

Preparations which are particularly preferred according to the invention preferably contain UV-B and UV-A-1 filters, as stated above. In principle, all UV filters can be used in combination with the color pigments according to the invention. Those UV filters whose physiological harmlessness has already been proven are particularly preferred. Both for UVA and UVB filters, there are many well-known and proven substances from the specialist literature, e.g.

Benzylidene camphor derivatives such as 3- (4 ^' -methylbenzylidene) -dl-camphor (e.g. Eusolex® 6300), 3-benzylidene camphor (e.g. Mexoryl® SD), polymers of N - {(2 and 4) - [(2-oxobom-3- yliden) methyl] benzyl} -acrylamide (e.g. Mexoryl® SW), N, N, N-trimethyl-4- (2-oxobom-3-ylidenmethyl) anilinium methyl sulfate (e.g. Mexoryl® SK) or (2-oxobom-3- ylidene) toluene-4-sulfonic acid (e.g. Mexoryl® SL),

Benzoyl- or dibenzoylmethanes such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione (e.g. Eusolex® 9020) or 4-

Isopropyldibenzoylmethane (e.g. Eusolex® 8020),

Benzophenones such as 2-hydroxy-4-methoxybenzophenone (e.g. Eusolex® 4360) or 2-hydroxy-4-methoxybenzophenone-5-su.fonic acid and its sodium salt (e.g. Uvinul® MS-40),

Methoxycinnamic acid esters such as octyl methoxycinnamate (e.g. Eusolex® 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of the isomers (e.g. Neo Heliopan® E 1000),

Salicylate derivatives such as 2-ethylhexyl salicylate (e.g. Eusolex® OS), 4-

Isopropyl benzyl salicylate (e.g. Megasol®) or 3,3,5-trimethylcyclohexyl salicylate (e.g. Eusolex® HMS),

4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 4-

(Dimethylamino) 2-ethylhexyl benzoate (e.g. Eusolex® 6007), ethoxylated 4-aminobenzoate (e.g. Uvinul® P25), Phenylbenzimidazole sulfonic acids, such as 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts (e.g. Eusolex® 232), 2,2- (1,4-phenylene) bisbenzimidazole-4,6-disulfonic acid or their salts ( eg Neoheliopan® AP) or 2,2- (1,4-phenylene) bisbenzimidazole-6-sulfonic acid;

and other substances like

2-Cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester (e.g. Eusolex® OCR), 3,3 ^' - (1, 4-phenylene dimethylene) -bis- (7,7-dimethyl-2-oxobicyclo- [2.2.1 ] hept-1-ylmethanesulfonic acid and its salts (eg Mexoryl® SX) and

2,4,6-trianilino- (p-carbo-2 ^{'-ethylhexyl-r-oxy)} -1, 3,5-triazine (for example Uvinul

T 150)

2- (4-Diethylamino-2-hydroxy-benzoyl) benzoic acid hexyl ester (e.g.

Uvinul®UVA Plus, from BASF).

The compounds in the list are only examples. Of course, other UV filters can also be used.

These organic UV filters are generally incorporated into cosmetic formulations in an amount of 0.5 to 10 percent by weight, preferably 1-8%.

Other suitable organic UV filters are e.g.

2- (2H-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1, 3,3,3-tetramethyl-1 - (trimethylsilyloxy) disiloxanyl) propyl) phenol (e.g. Silatrizole ^® )

4,4 ^' - [(6- [4 - ((1, 1-dimethylethyl) aminocarbonyl) phenylamino] -1, 3,5-triazine-2,4-diyl) diimino] bis (2-ethylhexyl benzoate) ( e.g. Uvasorb ^® HEB), - (trimethylsilyl) -ω- [trimethylsilyl) oxy] poly [oxy (dimethyl [and approx. 6% methyl [2- [p- [2,2-bis (ethoxycarbonyl] vinyl] phenoxy] - 1-methyleneethyl] and approx. 1.5% methyl [3- [p- [2,2-bis (ethoxycarbonyl) vinyl) phenoxy) propenyl) and 0.1 to

0.4% (methylhydrogenjsilylen]] (n «60) (CAS No. 207 574-74-1) 2,2 ^' -methylene-bis- (6- (2H-benzotriazol-2-yl) -4- ( 1, 1, 3,3-tetramethyl-butyl) phenol) (CAS No. 103 597-45-1) 2,2 '- (1, 4-phenylene) bis- (1 H-benzimidazole-4,6- disulfonic acid, monosodium salt) (CAS No. 180 898-37-7) and

2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxyl] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (CAS No. 103 597-45 -, 187 393-00-6).

4,4 ^' - [(6- [4 - ((1, 1-dimethylethyl) aminocarbonyl) phenylamino] -1, 3,5-triazine-2,4-diyl) diimino] bis (2-ethylhexyl benzoate) ( e.g. Uvasorb ^® HEB), Organic UV filters are generally incorporated into cosmetic formulations in an amount of 0.5 to 20 percent by weight, preferably 1-15%.

Conceivable inorganic UV filters are those are possible from the group of titanium dioxides, such as coated titanium dioxide (for example Eusolex® T-2000, Eusolex ^® T-AQUA), zinc oxides (eg Sachtotec.RTM), iron oxides and also cerium oxides. These inorganic UV filters are generally incorporated into cosmetic preparations in an amount of 0.5 to 20 percent by weight, preferably 2 to 10%.

Preferred compounds with UV-filtering properties are 3- (4'-methylbenzylidene) -dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxy-phenyl) -pro-pan-1, 3-dione , 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenbenzophenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclo-hexyl-salicylate, 4-

(Dimethylamino) 2-ethylhexyl benzoate, 2-cyano-3,3-di-phenyl-acrylic acid, 2-ethylhexyl ester, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanol amine salts.

Optimized compositions can, for example, combine the organic UV filters 4'-methoxy-6-hydroxyflavon with 1 - (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione and 3- (4 ^' -Methylbenzyliden) -dl-camphor contain. This combination provides broadband protection, which can be supplemented by adding inorganic UV filters such as titanium dioxide microparticles.

All of the UV filters mentioned can also be used in encapsulated form. In particular, it is advantageous to use encapsulated organic UV filters. The individual advantages are as follows:

- The hydrophilicity of the capsule wall can be independent of the solubility of the

UV filters can be set. For example, hydrophobic UV filters can also be incorporated into purely aqueous preparations. In addition, the oily impression, which is often perceived as unpleasant, is prevented when the preparation containing the hydrophobic UV filter is applied.

Certain UV filters, in particular dibenzoylmethane derivatives, show only a reduced photostability in cosmetic preparations. By encapsulating these filters or compounds that increase photostability these filters affect, such as cinnamic acid derivatives, the photostability of the entire preparation can be increased.

Skin penetration through organic UV filters and the associated potential for irritation when applied directly to human skin are repeatedly discussed in the literature. This effect is prevented by the encapsulation of the corresponding substances proposed here.

- Generally, by encapsulating individual UV filters or others

Preparation problems that arise from the interaction of individual preparation components with one another, such as crystallization processes, precipitations and agglomerate formation, are avoided since the interaction is prevented.

Suitable capsules can have walls made of inorganic or organic polymers. For example, US 6,242,099 B1 describes the production of suitable capsules with walls made of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules to be used particularly preferably according to the invention have walls which can be obtained by a SolGel process, as described in the applications WO 00/09652, WO 00/72806 and WO 00/71084. Again, capsules are preferred, the walls of which are made of silica gel (silica; undefined silicon oxide hydroxide). The production of corresponding capsules is known to the person skilled in the art, for example from the cited patent applications, the content of which expressly belongs to the subject of the present application.

The capsules in the preparations according to the invention are preferably present in amounts which ensure that the encapsulated UV filters are present in the preparation in the amounts indicated above.

A protective effect against oxidative stress or against the action of radicals can be achieved if the preparations contain one or more antioxidants.

There are many proven substances known from the specialist literature that can be used as antioxidants, for example amino acids (for example glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (for example urocanic acid) and their derivatives, peptides such as D, L- Camosin, D-Carnosin, L-Camosin and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, Cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and theirs Salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, himinathinsins very low dosages) pmol to μ mol / kg), furthermore (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, Bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (eg vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordohydroguajaretic acid, trihydroxy-unditrophin derivatives, mannose, quand Derivatives, zinc and its derivatives (eg ZnO, ZnS0 ₄ ), selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercially available mixtures are, for example, mixtures containing lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (eg Oxynex ^® AP), natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and Citric acid (e.g. Oxynex ^® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (e.g. Oxynex ^® L LIQUID), DL-α-tocopherol, L - (+) - Ascorbyl palmitate, citric acid and lecithin (eg Oxynex ^® LM) or butylated hydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (eg Oxynex ^® 2004). Such antioxidants are usually used in such compositions in ratios in the range from 1000: 1 to 1: 1000, preferably used in amounts of 100: 1 to 1: 100. The preparations according to the invention can contain vitamins as further ingredients. Vitamins and vitamin derivatives are preferably selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin Bi), riboflavin (vitamin B ₂ ), nicotinic acid amide, Vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D ₂ ), vitamin E, DL-α-tocopherol, tocopherol E-acetate, tocopherol hydrogen succinate, vitamin K. _f Esculin (vitamin P active ingredient), thiamine (vitamin Bi) , Nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin Bβ), pantothenic acid, biotin, folic acid and cobaltamine (vitamin B ₁₂ ) in the cosmetic preparations according to the invention, particularly preferably vitamin A palmitate, vitamin C, DL -α-tocopherol, tocopherol E-acetate, nicotinic acid, pantothenic acid and biotin. Vitamins are usually used with the color pigments according to the invention in ratios in the range from 1000: 1 to 1: 1000, preferably in amounts from 100: 1 to 1: 100.

The preparations according to the invention can also contain other customary skin-protecting or skin-care active ingredients. In principle, these can be all active ingredients known to the person skilled in the art.

Particularly preferred active ingredients are pyrimidine carboxylic acids and / or aryl oximes.

Pyrimidinecarboxylic acids occur in halophilic microorganisms and play a role in the osmoregulation of these organisms (E. A. Galinski et al., Eur. J. Biochem., 149 (1985) pages 135-139). Among the pyrimidinecarboxylic acids in particular are ectoin ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoin ((S, S) -1, 4,5,6-tetrahydro-5 -hydroxy-2-methyl-4-pyrimidinecarboxylic acid and its derivatives. These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic solvents. Furthermore, they particularly stabilize enzymes against denaturing conditions such as salts, extreme pH values, surfactants, urea , Guanidinium chloride and other compounds.

Ectoin and ectoin derivatives such as hydroxyectoin can advantageously be used in drugs. In particular, hydroxyectoin can be used to produce a medicament for the treatment of skin diseases. Other areas of application of hydroxyectoin and other ectoin derivatives are typically in areas where, for example, trehalose is used as an additive. Ectoin derivatives, such as hydroxyectoin, can be used as a protective agent in dried yeast and bacterial cells are used. Pharmaceutical products such as non-glycosylated, pharmaceutically active peptides and proteins, for example t-PA, can also be protected with ectoin or its derivatives.

Cosmetic applications include in particular the use of ectoin and ectoin derivatives for the care of aged, dry or irritated skin. For example, European patent application EP-A-0 671 161 describes in particular that ectoin and hydroxyectoin are used in cosmetic preparations such as powders, soaps, surfactant-containing cleaning products, lipsticks, blushes, make-ups, skin care creams and sunscreen preparations.

A pyrimidine carboxylic acid according to formula I below is preferably used,

wherein R ^{1 is} H or C1-8-alkyl, R ^{2 is} H or C1-4-alkyl and R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently a group from the group H, OH, NH ₂ and are C1-4 alkyl. Pyrimidinecarboxylic acids in which R ^{2 is} a methyl or an ethyl group and R ¹ or R ⁵ and R ^{6 are} H are preferably used. The pyrimidinecarboxylic acids ectoin ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidine-carboxylic acid) and hydroxyectoin ((S, S) -1, 4,5,6-tetrahydro- 5- hydroxy-2-methyl-4-pyrimidine-carboxylic acid) used. The preparations according to the invention preferably contain pyrimidinecarboxylic acids of this type in amounts of up to 15% by weight. The pyrimidinecarboxylic acids are preferably used in ratios of 100: 1 to 1: 100 to the color pigments according to the invention, ratios in the range 1:10 to 10: 1 being particularly preferred.

Among the aryl oximes, 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5, is preferably used. Its suitability for use in cosmetic products is known for example from German Offenlegungsschrift DE-A-41 16 123. Preparations which contain 2-hydroxy-5-methyllaurophenone oxime are therefore suitable for the treatment of skin diseases which are associated with inflammation. It is known that such preparations can be used, for example, for the therapy of psioriasis, various forms of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the appendages of the skin. Preparations according to the invention which, in addition to the color pigments according to the invention, additionally contain an aryl oxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising anti-inflammatory suitability. The preparations preferably contain 0.01 to 10% by weight of the aryloxime, it being particularly preferred if the preparation contains 0.05 to 5% by weight aryloxime.

All compounds or components that can be used in the preparations are either known and commercially available or can be synthesized by known methods.

The color pigments according to the invention can be incorporated into cosmetic preparations in the customary manner. Preparations are suitable for external use, for example as a cream, lotion, gel, or as a solution which can be sprayed onto the skin. Dosage formulas such as capsules, coated tablets, powders, tablet solutions or solutions are suitable for internal use.

As an application form of the compositions or preparations according to the invention, e.g. called: solutions, suspensions, emulsions, P IT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays. Other forms of application are e.g. Sticks, shampoos and shower baths. Any customary carriers, auxiliaries and, if appropriate, further active ingredients can be added to the preparation.

Preferred auxiliaries come from the group of preservatives, antioxidants, stabilizers, solubilizers, vitamins, colorants, odor improvers.

Ointments, pastes, creams and gels can contain the usual carriers, for example animal and vegetable fats, waxes, paraffins, starch, tragacanth, Cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.

Powders and sprays can contain the usual carriers, e.g. Milk sugar, talc, silica, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays can also contain the usual propellants, e.g. Chlorofluorocarbons, propane / butane or dimethyl ether.

Solutions and emulsions can contain the usual carriers such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1, 3-butyl glycol, oils, especially cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, glycerin fatty acid esters, polyethylene glycols and fatty acid esters of sorbitan contain.

Suspensions can be the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar agar and tragacanth or mixtures of these substances.

Soaps can contain the usual carriers such as alkali salts of fatty acids, salts of fatty acid half-esters, fatty acid protein hydrolyzates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugar or mixtures of these substances.

Surfactant-containing cleansing products may contain these substances, the customary excipients such as salts of fatty alcohol sulfates, Sulfobemsteinsäurehalbestem, fatty acid protein hydrolysates, isethionates, imidazolinium derivatives, methyl taurates, sarcosinates, Fettsäureamidethersulfate, alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated Glycerinfettsäureester or mixtures thereof.

Face and body oils can contain the usual carriers such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily plant extracts, paraffin oils, lanolin oils or mixtures of these substances. Other typical cosmetic application forms are also lipsticks, lip care sticks, mascara, eyeliner, eye shadows, blush, powder, emulsion and wax make-up as well as sun protection, pre-sun and after-sun preparations.

The preferred preparation forms according to the invention include, in particular, emulsions.

Emulsions according to the invention are advantageous and contain z. B. said fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as is usually used for such a type of preparation.

The lipid phase can advantageously be selected from the following group of substances:

Mineral oils, mineral waxes - oils, such as triglycerides of capric or caprylic acid, and also natural oils, such as, for. B. castor oil;

Fats, waxes and other natural and synthetic fat bodies, preferably esters of fatty acids with low C alcohols, e.g. With

Isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids;

Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes,

Diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms. atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethylaldehyde, 2-ethylaldehyde,

2-octyidodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate and synthetic,. semi-synthetic and natural mixtures of such esters, e.g. B. Jojoba oil. Furthermore, the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also fatty acid triglycerides, especially the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18, carbon atoms. The fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, e.g. As olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.

Advantageously, the oil phase selected from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _{_12-15} - alkyl benzoate, caprylic capric triglyceride, dicapryl ether.

Mixtures of C ₂ -i5 alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C ₂ -i ₅ alkyl benzoate and isotridecyl isononanoate and mixtures of C ₁₂ i5 alkyl benzoate, 2-ethyl hexyl isostearate and isotridecyl isononanoate are particularly advantageous.

Of the hydrocarbons, paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.

The oil phase can also advantageously have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane). Mixtures of cyclomethicone and isotridecyl isononanoate, cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous.

The aqueous phase of the preparations according to the invention optionally advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol,

Ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl,

-monoethyl or monobutyl ether, diethylene glycol monomethyl or

-monoethyl ether and analog products, furthermore alcohols of low C number, e.g. As ethanol, isopropanol, 1,2-propanediol, glycerin and in particular one or more

Thickeners, which one or which can advantageously be chosen from the

Group of silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g.

Hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984,

5984, each individually or in combination.

Mixtures of the abovementioned solvents are used in particular. Water can also be a component of alcoholic solvents.

Emulsions according to the invention are advantageous and contain z. B. said fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as is usually used for such a type of formulation.

In a preferred embodiment, the preparations according to the invention contain hydrophilic surfactants.

The hydrophilic surfactants are preferably selected from the group of alkyl glucosides, acyl lactylates, betaines and cocoamphoacetates.

The alkyl glucosides are in turn advantageously selected from the group of alkyl glucosides, which are characterized by the structural formula

distinguish, where R is a branched or unbranched alkyl radical having 4 to 24 carbon atoms and where DP is an average degree of glucosylation of up to 2.

The value DP represents the degree of glucosidation of the alkyl glucosides used according to the invention and is defined as

DP = 1 + ^■ 2 + 3 + ... = ∑ -

100 100 100 100

Pi, p ₂ , P3 ... and pj represent the proportion of single, double, triple ... i-fold glucosylated products in percentages by weight. Products with degrees of glucosylation of 1-2, particularly advantageously of 1, are advantageous according to the invention. 1 to 1, 5, very particularly advantageously selected from 1, 2-1, 4, in particular from 1, 3.

The value DP takes into account the fact that alkylglucosides are usually mixtures of mono- and oligoglucosides due to their production. A relatively high content of monoglucosides, typically of the order of 40-70% by weight, is advantageous according to the invention.

Alkylglylcosides which are used particularly advantageously according to the invention are selected from the group consisting of octylglucopyranoside, nonylglucopyranoside, decylglucopyranoside, undecylglucopyranoside, dodecylglucopyranoside, tetradecylglucopyranoside and hexadecylglucopyranoside.

It is also advantageous to use natural or synthetic raw materials and auxiliaries or mixtures which are distinguished by an effective content of the active compounds used according to the invention, for example Plantaren®

1200 (Henkel KGaA), Oramix ^® NS 10 (Seppic). The acyl lactylates are in turn advantageously selected from the group of substances which are characterized by the structural formula

CH,

1

R ¹ -C-0-CH

o o

M®

distinguish, wherein R ^{1 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M ^{+ is selected} from the group of alkali ions and the group of ammonium ions substituted with one or more alkyl and / or with one or more hydroxyalkyl radicals or half Equivalent to an alkaline earth ion.

Sodium isostearyl lactylate, for example the product, is advantageous

Pathionic ^® ISL from American Ingredients Company.

The betaines are advantageously selected from the group of substances which are distinguished by the structural formula

distinguish, wherein R ^{2 is} a branched or undisclosed alkyl radical having 1 to 30 carbon atoms.

R ² particularly advantageously denotes a branched or unbranched alkyl radical having 6 to 12 carbon atoms.

Capramidopropylbetaine, for example the product Tego ^® Betaine is advantageous, for example 810 from Th. Goldschmidt AG. , Sodium, for example, selected as inventively advantageous cocoamphoacetate as under the name Miranol ^® Ultra C32 from Miranol Chemical Corp. is available.

The preparations according to the invention are advantageously characterized in that the hydrophilic surfactant or surfactants in concentrations of 0.01-20% by weight, preferably 0.05-10% by weight, particularly preferably 0.1-5% by weight, in each case based on the total weight of the composition, is or are present.

For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.

Cosmetic and dermatological preparations according to the invention can be in various forms. So you can z. B. a solution, an anhydrous

Preparation, an emulsion or microemulsion of the water-in-oil (W / O) or oil-in-water (O W) type, a multiple emulsion, for example of the type

Waser-in-ÖI-in-Wasser (W / O / W), a gel, a solid stick, an ointment or an aerosol. It is also advantageous to give ectoine in an encapsulated form, e.g. B. in collagen matrices and other common encapsulation materials, eg. B. as cellulose encapsulations, encapsulated in gelatin, wax matrices or liposomal. In particular, wax matrices, as described in DE-OS 43 08 282, have proven to be favorable. To be favoured

Emulsions. O / W emulsines are particularly preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way.

For example, the known W / O and O / W emulsifiers can be used as emulsifiers. It is advantageous to use other customary co-emulsifiers in the preferred O / W emulsions according to the invention.

According to the invention, O / W emulsifiers are advantageously chosen as co-emulsifiers, primarily from the group of substances with HLB values of 11-16, very particularly advantageously with HLB values of 14.5-15.5, provided that the O / W emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers can also be lower or higher. It is advantageous to choose the fatty alcohol ethoxylates from the group of the ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols). Particularly preferred are: polyethylene glycol (13) stearyl ether (Steareth-13), polyethylene glycol (14) stearyl ether (Steareth-14), polyethylene glycol (15) stearyl ether (Steareth-15), polyethylene glycol (16) stearyl ether (Steareth-16), polyethylene glycol ( 17) - stearyl ether (steareth-17), polyethylene glycol (18) stearyl ether (steareth-18), polyethylene glycol (19) stearyl ether (steareth-19), polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (isosteareth -12), polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14) isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether (isosteareth-15), polyethylene glycol (16) isostearyl ether (isosteareth-16 ), Polyethylene glycol (17) isostearyl ether (isosteareth-17), polyethylene glycol (18) isostearyl ether (isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19), polyethylene glycol (20) isostearyl ether (isosteareth-20), polyethylene glycol ( 13) cetyl ether (ceteth-13), polyethylene glycol (14) cetyleth er (ceteth-14), polyethylene glycol (15) cetyl ether (ceteth-15), polyethylene glycol (16) cetyl ether (ceteth-16), polyethylene glycol (17) cetyl ether (ceteth-17), polyethylene glycol (18) cetyiether (ceteth-18) , Polyethylene glycol (19) cetyl ether (ceteth-19), polyethylene glycol (20) cety (ether (ceteth-20), polyethylene glycol (13) isocetyl ether (isoceteth-13), polyethylene glycol (14) isocetyl ether (isoceteth-14) , Polyethylene glycol (15) isocetyl ether (isoceteth-15), polyethylene glycol (16) - isocetyl ether (isoceteth-16), polyethylene glycol (17) isocetyIether (isoceteth-17), polyethylene glycol (18) isocetyl ether (isoceteth-18), polyethylene glycol isocetyl ether (isoceteth-19), polyethylene glycol (20) isocetyl ether (isoceteth-20), polyethylene glycol (12) oleyl ether (oleth-12), polyethylene glycol (13) oleyl ether (oleth-13), polyethylene glycol (14) oleyl ether (oleth- 14), polyethylene glycol (15) oleyl ether (oleth-15), polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) - isolauryl ether (isoIaureth-12), polyethylene glycol ( 13) cetyl stearyl ether (ceteareth-13), polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (ceteareth-15), polyethylene glycol (16) cetyl stearyl ether (ceteareth-16), polyethylene glycol (17) cetyl stearyl Ceteareth-17), polyethylene glycol (18) cetyl stearyl ether (Ceteareth-18), polyethylene glycol (19) cetyl stearyl ether (Ceteareth-19), polyethylene glycol (20) cetyl stearyl ether (Ceteareth-20).

It is also advantageous to choose the fatty acid ethoxylates from the following group:

Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate, polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, Polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate 22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate, polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, polyethylene glycol (17) oleate, polyethylene glycol (18) oleate, polyethylene glycol (19) oleate, polyethylene glycol (20) oleate,

Sodium laureth-11 carboxylate can advantageously be used as the ethoxylated alkyl ether carboxylic acid or its salt. Sodium laureth 1-4 sulfate can advantageously be used as the alkyl ether sulfate. Polyethylene glycol (30) cholesteryl ether can advantageously be used as the ethoxylated cholesterol derivative. Polyethylene glycol (25) soyasterol has also proven itself. Polyethylene glycol (60) evening primrose glycerides can advantageously be used as ethoxylated triglycerides (evening primrose = evening primrose).

It is also advantageous to use the polyethylene glycol glycerol fatty acid esters from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate,

Polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate,

Polyethylene glycol (6) glyceryl caprate / cprinate, polyethylene glycol (20) glyceryl oleate, polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoat).

It is also favorable to choose the sorbitan esters from the group consisting of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.

The following optional W / O emulsifiers can be used:

Fatty alcohols with 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids a chain length of 8 to 24, in particular 12-18 C atoms, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol ether of saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 8 to 24, in particular 12-18 C atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18 C atoms, and sorbitan esters saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18 C atoms.

Particularly advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate,

Diglyceryl monostearate, diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate,

Propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate,

Sorbitan monocaprylate, sorbitan monoisooleate, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, isobehenyl alcohol,

Selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl monocaprylate.

Preparations preferred according to the invention are particularly suitable for protecting human skin against aging processes and against oxidative stress, i.e. against damage by radicals, such as e.g. generated by solar radiation, heat or other influences. It is available in various dosage forms commonly used for this application. It can be used in particular as a lotion or emulsion, such as a cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, are available as solid pins or are made up as aerosol.

The preparation can contain cosmetic adjuvants which are usually used in this type of preparation, such as, for example, thickeners, plasticizers, wetting agents, surfactants, emulsifiers, preservatives, anti-foaming agents, perfumes, waxes, lanolin, blowing agents, dyes and / or pigments which color the agent itself or the skin, and other ingredients commonly used in cosmetics. An oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof can be used as the dispersing or solubilizing agent. The particularly preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerin and sorbitol.

A preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and, in addition to the color pigments according to the invention, contains, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.

Further preferred embodiments are oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, in particular triglycerides of fatty acids, or oily alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and / or a polyol , such as glycerin, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.

The preparation according to the invention can also be in the form of an alcoholic gel which comprises one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerol, and a thickener, such as silica. The oily-alcoholic gels also contain natural or synthetic oil or wax.

The solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.

If a preparation is packaged as an aerosol, the usual propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generally used.

The cosmetic preparation can also be used to protect the hair against photochemical damage, to prevent changes in color shades, discoloration or damage of a mechanical nature. In this case, it is suitably packaged as a shampoo, lotion, gel or emulsion for rinsing, the respective preparation being applied before or after shampooing, before or after dyeing or decoloring or before or after the perm. A preparation can also be selected as a lotion or gel for styling and treatment, as a lotion or gel for brushing or laying a water wave, as a hair lacquer, permanent wave agent, dye or bleaching agent for the hair. In addition to the color pigments according to the invention, the preparation having light protection properties can contain various adjuvants used in this type of agent, such as surface-active agents, thickeners, polymers, plasticizers, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, anti-grease agents, dyes and / or Pigments that color the product itself or the hair or other ingredients commonly used for hair care.

The present invention further relates to a method for producing a preparation, which is characterized in that at least one color pigment according to the invention is mixed with a cosmetically or dermatologically suitable carrier. The preparations according to the invention can be produced using techniques which are well known to the person skilled in the art.

The following example is intended to illustrate the present invention.

Example:

In a 100 ml Erlenmeyer flask, 0.631 g of 2,4,6-triamino-2,4,6-triazine (= melamine) in 50 ml of deionized water and 0.5 ml of tetramethylammonium hydroxide solution were 2.5% at 70 ° C dissolved with stirring and mixed with 0.22 ml formaldehyde solution 37%. The clear solution was stirred for 15 minutes to ensure the formation of the methylol melamine. Then 2 g of Berlin blue were added to the solution. Immediately afterwards, the now blue suspension to initiate the coating process (polycondensation) was mixed with 0.3 ml of H ₂ 0 ₂ 30%. The pigment formed was washed with water and acetone by means of a centrifuge, dried and assessed. Compared to the untreated Berlin blue, the material coated with melamine shows a much more pleasant, "greasy-creamy" feeling on the skin.

Claims

claims:

1. Coated, non-platelet-shaped color pigment, characterized in that the pigment consists of an inorganic or organic, amorphous or partially crystalline material which is provided with at least one coating, each layer containing at least one hardened melamine-formaldehyde resin or from one such exists.

2. Color pigment according to claim 1, characterized in that it consists of iron (HI) - hexacyanoferrate (π) or chromium (_ TJ) oxide.

3. Color pigment according to claim 1 or 2, characterized in that the hardened melamine-formaldehyde resin one or more inorganic or organic dyes and / or one or more inorganic or organic UV

Contains absorber, the dyes being soluble in the medium in which the pigment is coated.

4. Color pigment according to claim 3, characterized in that the one or more dyes are contained in one or more inner layers containing melamine-formaldehyde resin and the one or more UV absorbers in one or more outer, melamine-formaldehyde resin containing layers are included.

5. Color pigment according to one or more of claims 1 to 4, characterized in that in addition to the outermost coating, essentially round, hardened melamine-formaldehyde resin particles are applied which contain one or more dyes and / or one or more UV absorbers or else are free of dyes and / or UV absorbers.

6. Color pigment according to one or more of claims 1 to 5, characterized in that the hardened melamine-formaldehyde resin of the outermost layer is modified with functional groups.

7. Color pigment according to claim 6, characterized in that the functional groups which modify the outermost layer are introduced via an amino-functional compound which, in addition to the amino group, has one or more further functional groups, in which this amino-functional compound participates in the polycondensation reaction between melamine and formaldehyde participates and is incorporated into the melamine-formaldehyde network via the amino function and the functional groups thus brought to the surface are further modified, if necessary.

8. Color pigment according to claim 6, characterized in that the hardened melamine-formaldehyde resin of the outermost layer is modified via the methylolamine or amino groups present in it with compounds reactive towards hydroxyl and / or amino groups with functionalization of the surface.

9. Color pigment according to one or more of claims 3 to 8, wherein at least one fluorescent dye and a further optionally fluorescent dye is contained in the melamine-formaldehyde resin as dyes, the further dye being contained in an amount which the pigment can be used alone this dye gives essentially no color or fluorescence.

10. A process for the production of a single or multiple coated non-platelet-shaped color pigment, characterized in that in a first step in a single coating containing a color pigment in a basic aqueous medium

Melamine and formaldehyde and / or methylolmelamine, which may optionally be alkoxylated, is suspended and in a second step, by lowering the pH in the acidic range

Crosslinking of the organic components is brought about and, in the case of a multiple coating, steps one and two with the product of the preceding one

Coating reaction can be repeated.

11. The method according to claim 10, characterized in that part of the melamine is replaced by other crosslinking molecules from the group consisting of "guanamines, phenols and ureas" and / or a part of the methylolmelamine is replaced by corresponding guanamine, phenol or urea analogs is.

12. The method according to claim 10 or 1 1, characterized in that before or during the crosslinking, inorganic or organic dyes and / or inorganic or organic UV absorbers are added.

13. The method according to claim 12, characterized in that at least one fluorescent dye and another optionally fluorescent dye is added as dyes, the further dye being added in an amount which gives the pigment essentially no color or fluorescence when this dye is added alone ,

14. The method according to one or more of claims 10 to 13, characterized in that the lowering of the pH into the acidic range is effected by means of hydrogen peroxide by oxidizing excess and / or unreacted and / or formaldehyde contained in the methylolmelamines.

15. The method according to one or more of claims 10 to 14, characterized in that in the last coating step in addition to melamine and formaldehyde and / or methylolmelamine, an amino-functional compound which has one or more functional groups in addition to the amino group, takes part in the polycondensation reaction, the amino-functional compound is incorporated into the melamine-formaldehyde network via the amino function and the functional groups thus brought to the surface are further modified if necessary.

16. The method according to one or more of claims 10 to 14, characterized in that the hardened melamine-formaldehyde resin of the outermost layer over the methylolamine or on the surface thereof Amino groups are reacted with compounds which have a group which is reactive towards hydroxyl and / or amino groups, in addition to one or more further functional groups.

17. Use of one or more of the coated non-platelet-shaped color pigment of claims 1 to 9 as effect pigments in cosmetic formulations and / or other products which are intended for application to the skin.

18. Compositions containing one or more of the coated non-platelet-shaped carrier materials of claims 1 to 9 as a color pigment.

19. Compositions according to claim 18 containing one or more of the coated non-platelet-shaped carrier materials of claims 1 to 9 as a color pigment, characterized in that the compositions are cosmetic preparations.